Coherent signal detection in the statistical polarization regime enables high-resolution nanoscale NMR spectroscopy
Nitrogen-vacancy (NV) centers in diamond have emerged as quantum sensors capable of detecting nuclear magnetic resonance (NMR) signals at unprecedented length scales, ranging from picoliter sample volumes down to single spins at the diamond surface. While high-resolution (few-hertz) coherent NV-NMR spectroscopy has been demonstrated at the micrometer scale, achieving comparable resolution at the nanometer scale has remained elusive. In this nanoscale regime, sensing relies on detecting stochastic spin noise from statistical polarization, where molecular diffusion in liquid samples severely broadens the spectrum and degrades resolution. Here, we demonstrate that coherent detection of signals from a hyperpolarized nanoscale sample overcomes this limitation, enabling single-digit hertz spectral resolution and the capacity to resolve scalar couplings. Finally, building on these results, we present a comparative analysis of the sensitivity of coherent versus spin-noise detection, identifying the regimes in which each performs best.